Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids

ABSTRACT

Highly acidic, stabilized peroxycarboxylic acid compositions are disclosed as having both improved antimicrobial efficacy in comparison to conventional peroxyoctanoic acid and peroxyacetic acid compositions for sanitizing applications, and improved transport and shipping stability. In particular, low odor and low/no VOC compositions having dual functionality as both acid wash and sanitizing compositions are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 16/747,189, filedJan. 20, 2020, which is a continuation of U.S. Ser. No. 15/019,050,filed Feb. 9, 2016, now U.S. Pat. No. 10,893,674, issued Jan. 19, 2021,which is a continuation of U.S. Ser. No. 14/584,148, filed Dec. 29,2014, now U.S. Pat. No. 9,288,992, issued Mar. 22, 2016, which is acontinuation of U.S. Ser. No. 13/785,044, filed Mar. 5, 2013, and arehereby incorporated by reference in their entirety. The entire contentsof these patent applications are hereby expressly incorporated herein byreference including, without limitation, the specification, claims, andabstract, as well as any figures, tables, or drawings thereof.

FIELD OF THE INVENTION

The invention relates to peroxycarboxylic acid compositions that areliable to exothermic decomposition which are stabilized under highlyacidic conditions (e.g. high mineral acid levels) to provide improvedtransport and/or storage according to the invention. The compositionsare also low odor and low/no VOC dual functioning acid wash andsanitizing peroxycarboxylic acid compositions. Still further, thestabilized compositions have improved antimicrobial efficacy incomparison to conventional mixed peroxycarboxylic acid compositions forsanitizing applications, while providing these additional benefits ofimproved safety for transport and/or storage.

BACKGROUND OF THE INVENTION

Peroxycarboxylic acids (i.e. peracids, such as peracetic acid) fall intothe chemical category of “organic peroxides” which in turn areclassified as self-reactive, self-heating substances. Self-reactivesubstances are strictly regulated by the US Department of Transportation(DOT) following the guidance of the UN Committee for the Transport ofDangerous Goods (TDG). Like the US DOT most local and nationalgovernments strictly observe the UN TDG guidance thus making their“guidance” essentially a world wide requirement. These guidances may befound in the UN document known as the “orange book,” titledRecommendations on the Transport Of Dangerous Goods, 5^(th) revisededition, 2009.

The concern about self-heating substances is that most decompositionprocesses accelerate as temperature rises and usually exponentially. Aself-heating process producing heat faster than it can cool is thedefinition of a runaway reaction. In the case of organic peroxides therunaway reaction is accompanied by the generation of large volumes ofgas and therefore poses an extreme explosion risk. It is therefore anabsolute requirement for purposes of safety, with the ancillary benefitof improving both shelf-life and quality, that the heat generating rateof the organic peroxide containing product not exceed the cooling rateof the package. In addition, since the cooling rates decrease withincreased volume, these self-heating rates limit a commercial packagesize which in turn limits commercial opportunities. If for example aproduct falls into UN category 5.2 (D), as do some organic peroxides,they may not be sold in packages with a volume greater than 50 kg. For acustomer consuming hundreds of kilograms of product per day such alimitation may be unacceptable.

In summary there are two aspects (and two sets of tests) of aprospective “self-reactive substance” to address, the first involves thecharacterization of the chemical (5.2 A, B, C, D, E, F or G) and thesecond set of tests assesses the chemistry in the proposed package ofcommerce. By testing the chemistry in the proposed commercial packagethe heat loss characteristics as well as the heat generatingcharacteristics are assessed at various “ambient” temperatures. Theminimum ambient temperature at which the chemistry self heats to exceedthe ambient by at least 6 degrees Celsius is defined as the “SelfAccelerating Decomposition Temperature” (SADT). Restrictions onshipping, storage (i.e. refrigeration requirements) come therefore notjust from the classification test but also the SADT. If for example thepackage has an SADT<45 degrees Celsius refrigeration is required. Arequirement of refrigeration, like classification can severely restrictcommercial opportunities.

Various factors impact the transportation and/or storage risk andtherefore a specific product is required to be transported below itsSADT. For example, the larger a container, the lower itssurface-to-volume ratio will be, resulting in less transmittal of heatto the surroundings container when undergoing thermal decomposition anda reduction in the SADT. This increases the risk of storing andtransporting peroxycarboxylic acid compounds susceptible to exothermicdecomposition within large containers. This hazard can be minimized bystoring and transporting such compositions in containers having beendiluted with one or more liquids. The diluted peroxycarboxylic acids canalso be formulated into suspensions, emulsions, or solutions. Aqueousemulsions or suspensions are generally considered safer formulations,because the active peroxide is dispersed in the water phase (e.g.suitable for removing heat of decomposing peroxide molecules, such as byconvection and/or evaporation). Thus commercially-availableperoxycarboxylic acids are usually sold in an equilibrium solution,containing the corresponding carboxylic acid to the peroxycarboxylicacid, hydrogen peroxide and water.

Storage and/or transportation containers may also be made of substancesthat can withstand the pressures resulting from the inevitable gaseousdecay products but they must also be made of inert or semi-inertmaterials. For aqueous organic peroxides the most common containers aremade of high density polyethylene or polypropylene fitted with ventedclosures. Corrosion sensitive steel for example is not used as it willcontaminate the product with transition metal ions such as Fe³⁺ whichare catalytical decay accelerants for most organic peroxides. Packagesrange in size from several gram bottles to bulk storage tanks dependinglargely on their classification and their package-specific SADTs. Stillfurther, peroxycarboxylic acid compositions can be transported underrefrigeration.

In non-refrigeration transport and storage it becomes almost an absolutenecessity to employ transition metal chelators or “stabilizers” to bothelevate the SADTs as well as to maximize the shelf-life and quality oforganic peroxides. These stabilizers can be used in peroxycarboxylicacid compositions to stabilize the compositions. For example,phosphonate based stabilizers, such as phosphoric acid and salts,pyrophosphoric acid and salts and 1-hydroxyethylidene-1,1-diphosphonicacid (HEDP) and salts, are the most commonly used stabilizers inperoxycarboxylic acid compositions. When used individually at asufficient concentration, these stabilizers can significantly improvethe stability of the peroxycarboxylic acid compositions, and for theconventional (i.e. non-highly acidic) peroxycarboxylic acidcompositions, the stability profile achieved with these stabilizersallows for the commercial transportation and use of these compositions.However, for peroxycarboxylic acid compositions with highly acidicformulations, including for example using strong mineral acids, thesestabilizers' efficacy is greatly reduced, in many instances the efficacyis essentially non-existant.

Accordingly, it is an objective of the claimed invention to developstabilized peroxycarboxylic acid compositions having reduced storageand/or transportation hazards.

In a particular aspect, the stabilized compositions which overcome thechallenges associated with the SADT of conventional peroxycarboxylicacid compositions. In addition these stabilizer compositions may evenaffect the DOT classification, providing in some cases an exemption fromthe typical UN “5.2” class for organic peracids to the reduced risk“5.1” classification.

A further object of the invention is to provide a stabilizedperoxycarboxylic acid composition suitable for storage and/or transportat temperatures of at least 50° C. without presenting SADT hazards.

A still further object of the invention is to provide a stabilized,highly acidic, mixed peroxycarboxylic acid composition utilizing aunique peracid stabilizing agent.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to stable peroxycarboxylic acidcompositions and uses thereof. An advantage of the invention is thatunconventionally acidic peroxycarboxylic acid compositions, includingmixed peracids, are stabilized without impacting antimicrobial and/orsanitizing efficacy of the compositions. It is an advantage of thepresent invention that the stabilized peroxycarboxylic acid compositionsprovide other benefits including low foam profile, improved materialcompatibility and allows for monitoring by conductivity and/or opticalsensors.

In an embodiment, the present invention is directed to a compositioncomprising: a C₁-C₂₂ carboxylic acid; a C₁-C₂₂ percarboxylic acid;hydrogen peroxide; and a stabilizing agent, wherein the stabilizingagent is a picolinic acid or a compound having the following Formula(IA):

-   -   wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b)        are independently hydrogen or (C₁-C₆)alkyl; R² is OH or        —NR^(2a)R^(2b), wherein R^(2a) and R^(2b) are independently        hydrogen or (C₁-C₆)alkyl; each R³ is independently (C₁-C₆)alkyl,        (C₂-C₆)alkenyl or (C₂-C₆)alkynyl; and n is a number from zero to        3; or a salt thereof;    -   or a compound having the following Formula (IB):

-   -   wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b)        are independently hydrogen or (C₁-C₆)alkyl; R² is OH or        —NR^(2a)R^(2b), wherein R^(2a) and R^(2b) are independently        hydrogen or (C₁-C₆)alkyl; each R³ is independently (C₁-C₆)alkyl,        (C₂-C₆)alkenyl or (C₂-C₆)alkynyl; and n is a number from zero to        3; or a salt thereof; and    -   wherein said composition has a pH at about 3 or less.

In a further embodiment, the present invention is directed to methods ofstoring and/or transporting a highly acidic, stabilized peroxycarboxylicacid composition comprising: storing the above composition, wherein saidcomposition retains at least about 80% of the C₁-C₂₂ percarboxylic acidactivity after storage of about 30 days at about 50° C. In a stillfurther aspect, the present invention is directed to a method fortransporting the highly acidic, stabilized percarboxylic acidcomposition, preferably in bulk, wherein the SADT of said composition iselevated to at least above 45° C. during transportation and/or storage.

In a still further embodiment, the present invention is directed tomethods of using highly acidic, stabilized peroxycarboxylic acidcomposition comprising: providing the peroxycarboxylic acid composition,contacting a surface or substrate with a use solution of the compositionfor sufficient time to reduce a microbial population, wherein said usesolution has a pH below about 4, and wherein the composition retains atleast about 80% of the C₁-C₂₂ peroxycarboxylic acid activity afterstorage of about 30 days at about 50° C.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph of the comparison of the SADT study of aDPA-stabilized peroxycarboxylic acid composition according to anembodiment of the invention with a phosphate based peroxycarboxylic acidcomposition.

FIG. 2 shows a graph of the comparison of the SADT study of aDPA-stabilized, highly acidic peroxycarboxylic acid compositionaccording to an embodiment of the invention with a phosphate based,highly acidic peroxycarboxylic acid composition.

FIGS. 3-4 show graphs of the comparison of the SADT study of a highlyacidic peracid composition, where the DPA-stabilizing agent according toembodiments of the invention provided sufficient stabilization, suchthat the self-heating effects were not sufficient to reach the oventemperature within the 7 day period.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The embodiments of this invention are not limited to particularstabilized peroxycarboxylic acid compositions and methods of using thesame, which can vary and are understood by skilled artisans. It isfurther to be understood that all terminology used herein is for thepurpose of describing particular embodiments only, and is not intendedto be limiting in any manner or scope. For example, as used in thisspecification and the appended claims, the singular forms “a,” “an” and“the” can include plural referents unless the content clearly indicatesotherwise. Further, all units, prefixes, and symbols may be denoted inits SI accepted form.

Numeric ranges recited within the specification are inclusive of thenumbers defining the range and include each integer within the definedrange. Throughout this disclosure, various aspects of this invention arepresented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges as well asindividual numerical values within that range. For example, descriptionof a range such as from 1 to 6 should be considered to have specificallydisclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numberswithin that range, for example, 1, 2, 3, 4, 5, and 6. This appliesregardless of the breadth of the range.

So that the present invention may be more readily understood, certainterms are first defined. Unless defined otherwise, all technical andscientific terms used herein have the same meaning as commonlyunderstood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materials similar, modified, orequivalent to those described herein can be used in the practice of theembodiments of the present invention without undue experimentation, thepreferred materials and methods are described herein. In describing andclaiming the embodiments of the present invention, the followingterminology will be used in accordance with the definitions set outbelow.

The term “about,” as used herein, refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

As used herein, the term “cleaning” refers to a method used tofacilitate or aid in soil removal, bleaching, microbial populationreduction, and any combination thereof. As used herein, the term“microorganism” refers to any noncellular or unicellular (includingcolonial) organism. Microorganisms include all prokaryotes.Microorganisms include bacteria (including cyanobacteria), spores,lichens, fungi, protozoa, virinos, viroids, viruses, phages, and somealgae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

The term “hard surface” refers to a solid, substantially non-flexiblesurface such as a counter top, tile, floor, wall, panel, window,plumbing fixture, kitchen and bathroom furniture, appliance, engine,circuit board, and dish. Hard surfaces may include for example, healthcare surfaces and food/plant/animal processing surfaces.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid.

For the purpose of this patent application, successful microbialreduction is achieved when the microbial populations are reduced by atleast about 50%, or by significantly more than is achieved by a washwith water. Larger reductions in microbial population provide greaterlevels of protection. Differentiation of antimicrobial “-cidal” or“-static” activity, the definitions which describe the degree ofefficacy, and the official laboratory protocols for measuring thisefficacy are considerations for understanding the relevance ofantimicrobial agents and compositions. Antimicrobial compositions canaffect two kinds of microbial cell damage. The first is a lethal,irreversible action resulting in complete microbial cell destruction orincapacitation. The second type of cell damage is reversible, such thatif the organism is rendered free of the agent, it can again multiply.

The former is termed microbiocidal and the later, microbistatic. Asanitizer and a disinfectant are, by definition, agents which provideantimicrobial or microbiocidal activity. In contrast, a preservative isgenerally described as an inhibitor or microbistatic composition As usedherein, the term “sanitizer” refers to an agent that reduces the numberof bacterial contaminants to safe levels as judged by public healthrequirements. In an embodiment, sanitizers for use in this inventionwill provide at least a 99.999% reduction (5-log order reduction). Thesereductions can be evaluated using a procedure set out in Germicidal andDetergent Sanitizing Action of Disinfectants, Official Methods ofAnalysis of the Association of Official Analytical Chemists, paragraph960.09 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2).According to this reference a sanitizer should provide a 99.999%reduction (5-log order reduction) within 30 seconds at room temperature,25±2° C., against several test organisms.

As used herein, the term “sulfoperoxycarboxylic acid,” “sulfonatedperacid,” or “sulfonated peroxycarboxylic acid” refers to theperoxycarboxylic acid form of a sulfonated carboxylic acid. In someembodiments, the sulfonated peracids of the present invention aremid-chain sulfonated peracids. As used herein, the term “mid-chainsulfonated peracid” refers to a peracid compound that includes asulfonate group attached to a carbon that is at least one carbon (e.g.,the three position or further) from the carbon of the percarboxylic acidgroup in the carbon backbone of the percarboxylic acid chain, whereinthe at least one carbon is not in the terminal position. As used herein,the term “terminal position,” refers to the carbon on the carbonbackbone chain of a percarboxylic acid that is furthest from thepercarboxyl group.

The term “weight percent,” “wt-%,” “percent by weight,” “% by weight,”and variations thereof, as used herein, refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

The methods and compositions of the present invention may comprise,consist essentially of, or consist of the components and ingredients ofthe present invention as well as other ingredients described herein. Asused herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components or ingredients,but only if the additional steps, components or ingredients do notmaterially alter the basic and novel characteristics of the claimedmethods and compositions.

Compositions

While an understanding of the mechanism is not necessary to practice thepresent invention and while the present invention is not limited to anyparticular mechanism of action, it is contemplated that, in someembodiments, highly acidic peroxycarboxylic acid compositions are notsufficiently stabilized using conventional phosphate stabilizers.Phosphonate or other metal chelating stabilizers (e.g. HEDP/Dequest2010) are either incompatible and/or ineffective as stabilizers with thehighly acidic peracid compositions of the present invention, whichresults in SADT that effectively limit the transportation and/or storageof these self-accelerating decomposition compounds. The presentinvention provides peroxycarboxylic acid stabilizing compounds suitablefor use under highly acidic, equilibrium compositions. The presentinvention further provides peroxycarboxylic acid stabilizing compoundssuitable for use in compositions having extreme ratios of peracid tohydrogen peroxide, wherein the concentration of the peroxyacids greatlyexceed the hydrogen peroxide. In an embodiment, dipicolinic acid isprovided as the peroxycarboxylic acid stabilizer under strong acidicconditions in place of conventional peracid stabilizers, such as Dequest2010 which is predominantly used in commercial peracid products.Beneficially, the peroxycarboxylic acid stabilizer under strong acidicconditions elevates the SADT of the compositions providingtransportation and/or storage benefits.

According to an embodiment of the invention the stabilizedperoxycarboxylic acid compositions are suitable for storage and/ortransport at ambient temperatures that might occasionally reach about50° C. In an aspect, the stabilized composition retains at least about80% of the peroxycarboxylic acid activity after storage of about 30 daysat about 50° C. Preferably, the peracid compositions retain at leastabout 85%, at least about 90% or greater percentage of the peracidactivity after storage of about 30 days at about 50° C. According to afurther embodiment, the stabilized compositions can be transportedand/or stored, preferably in bulk, wherein the SADT of said compositionis elevated to at least about 45° C. during transportation, or to atleast about 50° C., or to at least about 60° C. (for moderate sizepackages) during transportation.

In an aspect, the compositions include concentrated equilibriumcompositions comprising a stabilizing agent, peracid(s), hydrogenperoxide, carboxylic acid(s), a solvent, e.g., water, and optionaladditional functional ingredients (e.g. defoaming agents, fluorescentactive compounds). In an aspect, the compositions include the exemplaryranges shown in Table 1 in weight percentage of the liquid concentratedequilibrium compositions.

TABLE 1 First Second Third Exemplary Exemplary Exemplary Range wt- Rangewt- Range wt- Material % % % Solvent (e.g. Water)  1-75 10-60 20-40Peroxycarboxylic Acid 0.1-40   1-40  1-20 Carboxylic Acid 0.1-90   1-80 1-50 Hydrogen Peroxide  1-90  1-80  1-50 Mineral Acid  1-50  1-20  5-20Stabilizing Agent 0.001-25   0.01-10   0.01-1   Additional Functional 0-25  0-20  0-10 Ingredients (e.g. defoaming agent)

In yet other aspects, the compositions according to the invention mayinclude non-equilibrium peracid compositions, such as where aperoxycarboxylic acid is generated in situ and/or on site through aprocess by one or more composition (e.g. one or more part systems)comprising individual reagents combined according to the invention. Inan exemplary aspect, these reagents are described herein individuallyalong and include at least one ester of a polyhydric alcohol and a C1 toC18 carboxylic acid, an oxidizing agent, a source of alkalinity,solvents, and other functional groups/agents. An acidulant is alsodescribed herein as a reagent to be added to the compositions after theformation of the percarboxylic acid(s). Alternatively, as describedherein, there may be benefits to providing the reagents in variouspremix formulations to decrease the number of reagents and/or increasethe simplicity of the invention for generating peracid compositions fora particular use. Premix formulations suitable for use according to theinvention may comprise, consist of and/or consist essentially of atleast one ester of a polyhydric alcohol and a C1 to C18 carboxylic acid,an oxidizing agent, a solvent and mixtures thereof. Premix formulationssuitable for use according to the invention may also comprise, consistof and/or consist essentially of at least one ester, an oxidizing agent,water, solvents, dispersing agents, surfactants, defoamers and mixturesthereof.

In some aspects the compositions, whether generated in situ or on sitefrom one or more premix compositions or whether provided in aconcentrated equilibrium composition, in a use solution have a pH atabout 4 or less. Preferably, the compositions in a use solution have apH at about 3 or less. In an aspect, the use solutions of the highlyacidic, stabilized peroxycarboxylic acid compositions, when dilutedpursuant to EPA sanitizer suspension preparations (e.g. dilute 1 oz. ofthe peracid composition to 8 Gallon with 500 ppm hard water), such thatthe pH of the solution is less than about 3.0, preferably between about2.8-2.9.

Peracid Stabilizing Agent

A peracid stabilizing agent or agents are included in compositionsaccording to the invention. Beneficially, the peracid stabilizing agentor agents prevent the decomposition of peracid in an equilibrium peracidcomposition. In addition, peracid stabilizing agent(s) prevent anequilibrium peracid composition from reaching their self-acceleratingdecomposition temperatures (SADT). The use of the peracid stabilizingagent beneficially stabilizes highly acidic equilibrium peracidsincluding mixed peracid compositions, as well as extreme chemistrieswith problematic high peracid to hydrogen peroxide ratios. By elevatingthe SADTs of the compositions the stabilizers contribute significantsafety benefits for transportation and storage of the compositions. Insome aspects, the stabilizing agents delay or prevent the compositionfrom meeting its native SADT.

In an aspect of the invention, the stabilizing agent is a pyridinecarboxylic acid compound. Pyridine carboxylic acids include dipicolinicacids, including for example, 2,6-pyridinedicarboxylic acid (DPA). In afurther aspect, the stabilizing agent is a picolinic acid, or a saltthereof.

In an aspect of the invention, the stabilizing agent is a picolinic acidor a compound having the following Formula (IA):

wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b) areindependently hydrogen or (C₁-C₆)alkyl; R² is OH or —NR^(2a)R^(2b),wherein R^(2a) and R^(2b) are independently hydrogen or (C₁-C₆)alkyl;each R³ is independently (C₁-C₆)alkyl, (C₂-C₆)alkenyl or (C₂-C₆)alkynyl;and n is a number from zero to 3; or a salt thereof.

In a further aspect of the invention, the peracid stabilizing agent is acompound having the following Formula (IB):

wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b) areindependently hydrogen or (C₁-C₆)alkyl; R² is OH or —NR^(2a)R^(2b),wherein R^(2a) and R^(2b) are independently hydrogen or (C₁-C₆)alkyl;each R³ is independently (C₁-C₆)alkyl, (C₂-C₆)alkenyl or (C₂-C₆)alkynyl;and n is a number from zero to 3; or a salt thereof.

In a preferred aspect, the peracid stabilizing agent is dipicolinic acid(picolinic acid, 2,6-Pyridinedicarboxylic acid) and providesstabilization for high mineral content peracids, wherein the resultingperacid composition has an elevated SADT.

Dipicolinic acid has been used as a stabilizer for peracid compositions,such as disclosed in WO 91/07375 and U.S. Pat. No. 2,609,391, which areherein incorporated by reference in their entirety. However, use of suchDPA stabilizer for peracid compositions has not previously beendisclosed and/or exploited for its SADT-elevating properties.

In a further aspect, the stabilizing agent may be combined withadditional conventional stabilizing agents, e.g. a phosphonate basedstabilizer, to beneficially provide further increase in stability of thecomposition, and in some aspects provide synergistic increase in SADTand peracid stability according to embodiments of the invention.

Stabilizing agents may be present in amounts sufficient to provide theintended stabilizing benefits, namely achieving the desired shelf life,and elevating the SADT of the highly acidic peroxycarboxylic acidcompositions having a use solution pH of below at least 4, preferablybelow at least 3. As the property of the composition will vary dependingupon the acidity of the particular peracid composition according to theinvention, such peracid stabilizing agents may be present in aconcentrated equilibrium peracid composition in amounts from about 0.001wt-% to about 25 wt-%, 0.01 wt-% to about 10 wt-%, and more preferablyfrom about 0.01 wt-% to about 1 wt-%. Without limiting the scope ofinvention, the numeric ranges are inclusive of the numbers defining therange and include each integer within the defined range.

Peracids

According to the invention, a peroxycarboxylic acid (i.e. peracid) isincluded for antimicrobial efficacy in the sanitizing compositionsdisclosed herein. As used herein, the term “peracid” may also bereferred to as a “percarboxylic acid,” “peroxycarboxylic acid” or“peroxyacid.” Sulfoperoxycarboxylic acids, sulfonated peracids andsulfonated peroxycarboxylic acids are also included within the terms“peroxycarboxylic acid” and “peracid” as used herein. The terms“sulfoperoxycarboxylic acid,” “sulfonated peracid,” or “sulfonatedperoxycarboxylic acid” refers to the peroxycarboxylic acid form of asulfonated carboxylic acid as disclosed in U.S. Pat. No. 8,344,026, andU.S. Patent Publication Nos. 2010/0048730 and 2012/0052134, each ofwhich are incorporated herein by reference in their entirety. As one ofskill in the art appreciates, a peracid refers to an acid having thehydrogen of the hydroxyl group in carboxylic acid replaced by a hydroxygroup. Oxidizing peracids may also be referred to herein asperoxycarboxylic acids.

A peracid includes any compound of the formula R—(COOOH)_(n) in which Rcan be hydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl,heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein.

As used herein, the term “alkyl” or “alkyl groups” refers to saturatedhydrocarbons having one or more carbon atoms, including straight-chainalkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, etc.), cyclic alkyl groups (or “cycloalkyl” or“alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups(e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), andalkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkylgroups and cycloalkyl-substituted alkyl groups). Preferably, a straightor branched saturated aliphatic hydrocarbon chain having from 1 to 22carbon atoms, such as, for example, methyl, ethyl, propyl, isopropyl(1-methylethyl), butyl, tert-butyl (1,1-dimethylethyl), and the like.

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate,alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

The term “alkenyl” includes an unsaturated aliphatic hydrocarbon chainhaving from 2 to 12 carbon atoms, such as, for example, ethenyl,1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, and the like.The alkyl or alkenyl can be terminally substituted with a heteroatom,such as, for example, a nitrogen, sulfur, or oxygen atom, forming anaminoalkyl, oxyalkyl, or thioalkyl, for example, aminomethyl, thioethyl,oxypropyl, and the like. Similarly, the above alkyl or alkenyl can beinterrupted in the chain by a heteroatom forming an alkylaminoalkyl,alkylthioalkyl, or alkoxyalkyl, for example, methylaminoethyl,ethylthiopropyl, methoxymethyl, and the like.

Further, as used herein the term “alicyclic” includes any cyclichydrocarbyl containing from 3 to 8 carbon atoms. Examples of suitablealicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentanyl,etc. In some embodiments, substituted alkyls can include a heterocyclicgroup. As used herein, the term “heterocyclic group” includes closedring structures analogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, forexample, nitrogen, sulfur or oxygen. Heterocyclic groups may besaturated or unsaturated. Exemplary heterocyclic groups include, but arenot limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan. Additional examples of suitable heterocyclicgroups include groups derived from tetrahydrofurans, furans, thiophenes,pyrrolidines, piperidines, pyridines, pyrrols, picoline, coumaline, etc.

According to the invention, alkyl, alkenyl, alicyclic groups, andheterocyclic groups can be unsubstituted or substituted by, for example,aryl, heteroaryl, C₁₋₄ alkyl, C₁₋₄ alkenyl, C₁₋₄ alkoxy, amino, carboxy,halo, nitro, cyano, —SO₃H, phosphono, or hydroxy. When alkyl, alkenyl,alicyclic group, or heterocyclic group is substituted, preferably thesubstitution is C₁₋₄ alkyl, halo, nitro, amido, hydroxy, carboxy,sulpho, or phosphono. In one embodiment, R includes alkyl substitutedwith hydroxy. The term “aryl” includes aromatic hydrocarbyl, includingfused aromatic rings, such as, for example, phenyl and naphthyl. Theterm “heteroaryl” includes heterocyclic aromatic derivatives having atleast one heteroatom such as, for example, nitrogen, oxygen, phosphorus,or sulfur, and includes, for example, furyl, pyrrolyl, thienyl,oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl,isothiazolyl, etc. The term “heteroaryl” also includes fused rings inwhich at least one ring is aromatic, such as, for example, indolyl,purinyl, benzofuryl, etc.

According to the invention, aryl and heteroaryl groups can beunsubstituted or substituted on the ring by, for example, aryl,heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxy, halo, nitro, cyano,—SO₃H, phosphono, or hydroxy. When aryl, aralkyl, or heteroaryl issubstituted, preferably the substitution is C₁₋₄ alkyl, halo, nitro,amido, hydroxy, carboxy, sulpho, or phosphono. In one embodiment, Rincludes aryl substituted with C₁₋₄ alkyl.

Peracids suitable for use include any peroxycarboxylic acids, includingvarying lengths of peroxycarboxylic acids (e.g. C1-22) that can beprepared from the acid-catalyzed equilibrium reaction between acarboxylic acid described above and hydrogen peroxide. Aperoxycarboxylic acid can also be prepared by the auto-oxidation ofaldehydes or by the reaction of hydrogen peroxide with an acid chloride,acid anhydride, carboxylic acid anhydride, sodium alcoholate or alkyland aryl esters. Alternatively, peracids can be prepared throughnon-equilibrium reactions, which may be generated for use in situ, suchas the methods disclosed in U.S. Patent Publication Nos. 2012/0172440and 2012/0172441 each titled “In Situ Generation of PeroxycarboxylicAcids at Alkaline pH, and Methods of Use Thereof,” which areincorporated herein by reference in their entirety. Preferably acomposition of the invention includes peroxyacetic acid, peroxyoctanoicacid, peroxypropionic acid, peroxylactic acid, peroxyheptanoic acid,peroxyoctanoic acid and/or peroxynonanoic acid.

In some embodiments, a peroxycarboxylic acid includes at least onewater-soluble peroxycarboxylic acid in which R includes alkyl of 1-22carbon atoms. For example, in one embodiment, a peroxycarboxylic acidincludes peroxyacetic acid. In another embodiment, a peroxycarboxylicacid has R that is an alkyl of 1-22 carbon atoms substituted with ahydroxyl group or other polar substituent such that the substituentimproves the water solubility. Methods of preparing peroxyacetic acidare known to those of skill in the art including those disclosed in U.S.Pat. No. 2,833,813, which is herein incorporated herein by reference inits entirety.

In another embodiment, a sulfoperoxycarboxylic acid has the followingformula:

wherein R₁ is hydrogen, or a substituted or unsubstituted alkyl group;R₂ is a substituted or unsubstituted alkylene group; X is hydrogen, acationic group, or an ester forming moiety; or salts or esters thereof.In some embodiments, R₁ is a substituted or unsubstituted Cm alkylgroup; X is hydrogen a cationic group, or an ester forming moiety; R₂ isa substituted or unsubstituted C_(n) alkyl group; m=1 to 10; n=1 to 10;and m+n is less than 18, or salts, esters or mixtures thereof.

In some embodiments, R₁ is hydrogen. In other embodiments, R₁ is asubstituted or unsubstituted alkyl group. In some embodiments, R₁ is asubstituted or unsubstituted alkyl group that does not include a cyclicalkyl group. In some embodiments, R₁ is a substituted alkyl group. Insome embodiments, R₁ is an unsubstituted C₁-C₉ alkyl group. In someembodiments, R₁ is an unsubstituted C₇ or C₈ alkyl. In otherembodiments, R₁ is a substituted C₅-C₁₀ alkylene group. In someembodiments, R₁ is a substituted C₅-C₁₀ alkyl group is substituted withat least 1, or at least 2 hydroxyl groups. In still yet otherembodiments, R₁ is a substituted C₁-C₉ alkyl group. In some embodiments,R₁ is a substituted C₁-C₉ substituted alkyl group is substituted with atleast 1 SO₃H group. In other embodiments, R₁ is a C₉-C₁₀ substitutedalkyl group. In some embodiments, R₁ is a substituted C₉-C₁₀ alkyl groupwherein at least two of the carbons on the carbon backbone form aheterocyclic group. In some embodiments, the heterocyclic group is anepoxide group.

In some embodiments, R₂ is a substituted C₁-C₁₀ alkylene group. In someembodiments, R₂ is a substituted C₅-C₁₀ alkylene. In some embodiments,R₂ is an unsubstituted C₆-C₉ alkylene. In other embodiments, R₂ is aC₅-C₁₀ alkylene group substituted with at least one hydroxyl group. Insome embodiments, R₂ is a C₁₀ alkylene group substituted with at leasttwo hydroxyl groups. In other embodiments, R₂ is a C₈ alkylene groupsubstituted with at least one SO₃H group. In some embodiments, R₂ is asubstituted C₉ group, wherein at least two of the carbons on the carbonbackbone form a heterocyclic group. In some embodiments, theheterocyclic group is an epoxide group. In some embodiments, R₁ is aC₈-C₉ substituted or unsubstituted alkyl, and R₂ is a C₇-C₈ substitutedor unsubstituted alkylene.

These and other suitable sulfoperoxycarboxylic acid compounds for use inthe stabilized peroxycarboxylic acid compositions of the invention arefurther disclosed in U.S. Pat. No. 8,344,026 and U.S. Patent PublicationNos. 2010/0048730 and 2012/0052134, which are incorporated herein byreference in its entirety.

In additional embodiments a sulfoperoxycarboxylic acid is combined witha single or mixed peroxycarboxylic acid composition, such as asulfoperoxycarboxylic acid with peroxyacetic acid and peroxyoctanoicacid (PSOA/POOA/POAA). In other embodiments, a mixed peracid isemployed, such as a peroxycarboxylic acid including at least oneperoxycarboxylic acid of limited water solubility in which R includesalkyl of 5-22 carbon atoms and at least one water-solubleperoxycarboxylic acid in which R includes alkyl of 1-4 carbon atoms. Forexample, in one embodiment, a peroxycarboxylic acid includesperoxyacetic acid and at least one other peroxycarboxylic acid such asthose named above. Preferably a composition of the invention includesperoxyacetic acid and peroxyoctanoic acid, such as disclosed in U.S.Pat. No. 5,314,687 which is herein incorporated by reference in itsentirety. In an aspect, the peracid mixture is a hydrophilic peraceticacid and a hydrophobic peroctanoic acid, providing antimicrobialsynergy. In an aspect, the synergy of a mixed peracid system allows theuse of lower dosages of the peracids.

In another embodiment, a tertiary peracid mixture composition, such asperoxysulfonated oleic acid, peracetic acid and peroctanoic acid areemployed, such as disclosed in U.S. Pat. No. 8,344,026 which isincorporated herein by reference in its entirety. Advantageously, acombination of peroxycarboxylic acids provides a composition withdesirable antimicrobial activity in the presence of high organic soilloads. The mixed peroxycarboxylic acid compositions often providesynergistic micro efficacy. Accordingly, compositions of the inventioncan include a peroxycarboxylic acid, or mixtures thereof.

Various commercial formulations of peracids are available, including forexample peracetic acid (approximately 15%) available as EnviroSan(Ecolab, Inc., St. Paul Minn.). Most commercial peracid solutions statea specific percarboxylic acid concentration without reference to theother chemical components in a use solution. However, it should beunderstood that commercial products, such as peracetic acid, will alsocontain the corresponding carboxylic acid (e.g. acetic acid), hydrogenperoxide and water.

In an aspect, any suitable C₁-C₂₂ percarboxylic acid can be used in thepresent compositions. In some embodiments, the C₁-C₂₂ percarboxylic acidis a C₂-C₂₀ percarboxylic acid. In other embodiments, the C₁-C₂₂percarboxylic is a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂,C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ carboxylic acid. Instill other embodiments, the C₁-C₂₂ percarboxylic acid comprisesperoxyacetic acid, peroxyoctanoic acid and/or peroxysulfonated oleicacid.

In an aspect of the invention, a peracid may be selected from aconcentrated composition having a ratio of hydrogen peroxide to peracidfrom about 0:10 to about 10:0, preferably from about 0.5:10 to about10:0.5, preferably from about 1:8 to 8:1. Various concentrated peracidcompositions having the hydrogen peroxide to peracid ratios of about0.5:10 to about 10:0.5, preferably from about 1:8 to 8:1, may beemployed to produce a use solution for treatment according to themethods of the invention. In a further aspect of the invention, aperacid may have a ratio of hydrogen peroxide to peracid as low as fromabout 0.01 part hydrogen peroxide to about 1 part peracid. Withoutlimiting the scope of invention, the numeric ranges are inclusive of thenumbers defining the range and include each integer within the definedrange.

Obtaining the preferred hydrogen peroxide to peroxycarboxylic acidratios in a peracid composition may be obtained by a variety of methodssuitable for producing a very low hydrogen peroxide to peracid ratio. Inan aspect, equilibrium peracid compositions may be distilled to recovera very low hydrogen peroxide peracid mixture. In yet another aspect,catalysts for hydrogen peroxide decomposition may be combined with aperacid composition, including for example, peroxide-reducing agentsand/or other biomimetic complexes. In yet another aspect, perhydrolysisof peracid precursors, such as esters (e.g. triacetin) and amides may beemployed to obtain peracids with very low hydrogen peroxide. These andother methods of reducing hydrogen peroxide ratios in a peracidcomposition are disclosed in U.S. patent Publication Ser. No. 13/798,311(Ecolab 3031USU1) titled “Use of Peracetic Acid/Hydrogen Peroxide andCatalase for Treatment of Drilling Fluids, Frac Fluids, Flowback Waterand Disposal Water, and Ser. Nos. 13/798,281 and 13/798,307 (3031USI1and 3031USI2) titled “Use of Peracetic Acid/Hydrogen Peroxide andPeroxide Reducing Agents for Treatment of Drilling Fluids, Frac Fluids,Flowback Water and Disposal Water,” each of which are hereinincorporated by reference in their entirety.

In a preferred aspect, the C₁-C₂₂ percarboxylic acid can be used at anysuitable concentration. In some embodiments, the C₁-C₂₂ percarboxylicacid has a concentration from about 0.1 wt-% to about 40 wt-% in aconcentrated equilibrium composition. In other embodiments, the C₁-C₂₂percarboxylic acid has a concentration from about 1 wt-% to about 40wt-%, or from about 1 wt-% to about 20 wt-%. In still other embodiments,the C₁-C₂₂ percarboxylic acid has a concentration at about 1 wt-%, 2wt-%, 3 wt-%, 4 wt-%, 5 wt-%, 6 wt-%, 7 wt-%, 8 wt-%, 9 wt-%, 10 wt-%,11 wt-%, 12 wt-%, 13 wt-%, 14 wt-%, 15 wt-%, 16 wt-%, 17 wt-%, 18 wt-%,19 wt-%, 20 wt-%, 25 wt-%, 30 wt-%, 35 wt-%, or 40 wt-%. Withoutlimiting the scope of invention, the numeric ranges are inclusive of thenumbers defining the range and include each integer within the definedrange.

Carboxylic Acid

The present invention includes a carboxylic acid with the peracidcomposition and hydrogen peroxide. A carboxylic acid includes anycompound of the formula R—(COOH)_(n) in which R can be hydrogen, alkyl,alkenyl, alkyne, acylic, alicyclic group, aryl, heteroaryl, orheterocylic group, and n is 1, 2, or 3. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined above with respect to peracids.

Examples of suitable carboxylic acids according to the equilibriumsystems of peracids according to the invention include a varietymonocarboxylic acids, dicarboxylic acids, and tricarboxylic acids.Monocarboxylic acids include, for example, formic acid, acetic acid,propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoicacid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid,dodecanoic acid, glycolic acid, lactic acid, salicylic acid,acetylsalicylic acid, mandelic acid, etc. Dicarboxylic acids include,for example, adipic acid, fumaric acid, glutaric acid, maleic acid,succinic acid, malic acid, tartaric acid, etc. Tricarboxylic acidsinclude, for example, citric acid, trimellitic acid, isocitric acid,agaicic acid, etc.

In an aspect of the invention, a particularly well suited carboxylicacid is water soluble such as formic acid, acetic acid, propionic acid,butanoic acid, lactic acid, glycolic acid, citric acid, mandelic acid,glutaric acid, maleic acid, malic acid, adipic acid, succinic acid,tartaric acid, etc. Preferably a composition of the invention includesacetic acid, octanoic acid, or propionic acid, lactic acid, heptanoicacid, octanoic acid, or nonanoic acid. Additional examples of suitablecarboxylic acids are employed in sulfoperoxycarboxylic acid orsulfonated peracid systems, which are disclosed in U.S. Pat. No.8,344,026, and U.S. Patent Publication Nos. 2010/0048730 and2012/0052134, each of which are herein incorporated by reference intheir entirety.

Any suitable C₁-C₂₂ carboxylic acid can be used in the presentcompositions. In some embodiments, the C₁-C₂₂ carboxylic acid is aC₂-C₂₀ carboxylic acid. In other embodiments, the C₁-C₂₂ carboxylic acidis a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, C₁₄, C₁₅,C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ carboxylic acid. In still otherembodiments, the C₁-C₂₂ carboxylic acid comprises acetic acid, octanoicacid and/or sulfonated oleic acid.

The C₁-C₂₂ carboxylic acid can be used at any suitable concentration. Insome embodiments, the C₁-C₂₂ carboxylic acid has a concentration in anequilibrium composition from about 0.1 wt-% to about 90 wt-%. In otherembodiments, the C₁-C₂₂ carboxylic acid has a concentration from about 1wt-% to about 80 wt-%. In still other embodiments, the C₁-C₂₂ carboxylicacid has a concentration at about 1 wt-% to about 50 wt-%. Withoutlimiting the scope of invention, the numeric ranges are inclusive of thenumbers defining the range and include each integer within the definedrange.

Hydrogen Peroxide

The present invention includes hydrogen peroxide. Hydrogen peroxide,H₂O₂, provides the advantages of having a high ratio of active oxygenbecause of its low molecular weight (34.014 g/mole) and being compatiblewith numerous substances that can be treated by methods of the inventionbecause it is a weakly acidic, clear, and colorless liquid. Anotheradvantage of hydrogen peroxide is that it decomposes into water andoxygen. It is advantageous to have these decomposition products becausethey are generally compatible with substances being treated. Forexample, the decomposition products are generally compatible withmetallic substance (e.g., substantially noncorrosive) and are generallyinnocuous to incidental contact and are environmentally friendly.

In one aspect of the invention, hydrogen peroxide is initially in anantimicrobial peracid composition in an amount effective for maintainingan equilibrium between a carboxylic acid, hydrogen peroxide, and aperacid. The amount of hydrogen peroxide should not exceed an amountthat would adversely affect the antimicrobial activity of a compositionof the invention. In further aspects of the invention, hydrogen peroxideconcentration can be significantly reduced within an antimicrobialperacid composition. In some aspects, an advantage of minimizing theconcentration of hydrogen peroxide is that antimicrobial activity of acomposition of the invention is improved as compared to conventionalequilibrium peracid compositions.

The hydrogen peroxide can be used at any suitable concentration. In someembodiments, a concentrated equilibrium composition has a concentrationof hydrogen peroxide from about 0.5 wt-% to about 90 wt-%, or from about1 wt-% to about 90 wt-%. In still other embodiments, the hydrogenperoxide has a concentration from about 1 wt-% to about 80 wt-%, fromabout 1 wt-% to about 50 wt-%. Without limiting the scope of invention,the numeric ranges are inclusive of the numbers defining the range andinclude each integer within the defined range.

Beneficially, the compositions and methods of the invention in providingstabilized equilibrium peracid compositions, are not reliant and/orlimited according to any particular ratio of hydrogen peroxide toperacid for such enhanced stability. Instead, it is unexpected that thestabilizing agent (e.g. DPA) is suitable for providing peracid stabilityunder high acidity/mineral acid conditions, while constraining theperacid SADT. This represents a significant improvement over the priorart, wherein DPA is an optional peracid stabilizing agent for lowhydrogen peroxide containing peracid compositions. See e.g. U.S.Publication No. 2010/021558, which is herein incorporated by referencein its entirety.

Mineral Acid

In some embodiments, the present composition is a strongly acidicperacid as a result of inclusion of a strong acid. In some aspects theperacid composition has a use solution pH of 4 or less, and preferablyhas a use solution pH of 3 or less. In some embodiments, the presentcomposition includes an inorganic acid. In preferred embodiments, thepresent composition includes a mineral acid.

Particularly suitable mineral acids include sulfuric acid (H₂SO₄),sodium hydrogen sulfate, nitric acid, sulfamic acid and sulfonic acidsboth alkyl and aryl, in particular methane sulfonic acid anddodecylbenzene, toluene, xylene, naphthalene and cumene sulfonic acid,and/or phosphoric acid (H₃PO₄). Additional phosphonic acids which may beused according to the invention include, for example, aminotrimethylenephosphonic acid, ethylene diamin tetramethylene phosphonic acid,hexamethylene diamin tetramethylene phosphonic acid, diethylene triamintetramethylene phosphonic acid, and 1-hydroxyethylidene-1,1-diphosphonicacid (HEDP).

In a further aspect, the acids suitable for use include are not limitedto mineral acids. Instead, acids suitable for use include strong acids,which are defined as those with a pKa near or below the lower pKas ofHEDP which may cause significant protonation of the HEDP and otherphosphate and phosphonate stabilizers and thus diminish their ability tostabilize the peracid chemistries. Additional description of mineralacids for use in peracid compositions is disclosed in WO 91/07375, whichis herein incorporated by reference in its entirety.

In an aspect of the invention, the mineral acid providing the strongacidity of the peracid compositions can be used at any suitableconcentration. In some embodiments, a concentrated equilibriumcomposition has a concentration of the mineral acid from about 0.5 wt-%to about 50 wt-%, or from about 1 wt-% to about 50 wt-%. In still otherembodiments, the mineral acid has a concentration from about 1 wt-% toabout 20 wt-%, or more preferably from about 5 wt-% to about 20 wt-%.Without limiting the scope of invention, the numeric ranges areinclusive of the numbers defining the range and include each integerwithin the defined range.

Additional Functional Ingredients

In some embodiments, the present composition can further compriseadditional functional ingredients. In some embodiments, the highlyacidic peracid composition including the stabilizing agent, mineralacid, peroxycarboxylic acid, carboxylic acid, hydrogen peroxide andwater make up a large amount, or even substantially all of the totalweight of the peracid compositions. For example, in some embodiments fewor no additional functional ingredients are disposed therein.

In other embodiments, additional functional ingredients may be includedin the compositions. The functional ingredients provide desiredproperties and functionalities to the compositions. For the purpose ofthis application, the term “functional ingredient” includes a materialthat when dispersed or dissolved in a use and/or concentrate solution,such as an aqueous solution, provides a beneficial property in aparticular use. Some particular examples of functional materials arediscussed in more detail below, although the particular materialsdiscussed are given by way of example only, and that a broad variety ofother functional ingredients may be used. In some aspects, thecompositions may include defoaming agents, surfactants, additionalantimicrobial agents, anti-redeposition agents, bleaching agents,solubility modifiers, dispersants, rinse aids, metal protecting agents,stabilizing agents, corrosion inhibitors, fragrances and/or dyes,rheology modifiers or thickeners, hydrotropes or couplers, buffers,solvents and the like.

In preferred embodiments, the compositions further include substancesthat aid in the solubilization of the stabilizing agent(s), includingfor example, hydrotropes such as sodium xylene sulfonate (SXS), sodiumcumene sulfonates (SCS), surfactants, such as anionic surfactants andnoinionic surfactants, and a defoaming agent. In further aspects, thecomposition may utilize alternative hydrotropes for solubilization ofthe stabilizing agent, including for example, n-octanesulfonate, axylene sulfonate, a naphthalene sulfonate, ethylhexyl sulfate, laurylsulfate, an amine oxide, etc.

In preferred embodiments, the compositions do not include phosphonicacid based stabilizers (e.g. pyrophosphoric acids and/or salts thereof,HEDP, (H_(n+2)PnO_(3n+1))).

Surfactants

In some embodiments, the compositions of the present invention include asurfactant. Surfactants suitable for use with the compositions of thepresent invention include, but are not limited to nonionic surfactantsand/or anionic surfactants. Preferably, a low foaming anionic surfactantis included in the peroxycarboxylic acid compositions. Beneficially,according to embodiments of the invention, the use of the defoamingagent (e.g. aluminum sulfate) in combination with the surfactantovercomes the foaming issues that are known to result from the use ofconventional low-foaming surfactants in peroxycarboxylic acidcompositions, especially in deionized or soft water.

In some embodiments, the compositions of the present invention includeabout 0 wt-% to about 40 wt-% of a surfactant. In other embodiments thecompositions of the present invention include about 0.1 wt-% to about 40wt-% of a surfactant, preferably from about 0.1 wt-% to about 25 wt-% ofa surfactant, and more preferably from about 1 wt-% to about 20 wt-% ofa surfactant.

Anionic Surfactants

Preferably, surface active substances which are categorized as anionicsbecause the charge on the hydrophobe is negative are utilized accordingto the present invention; or surfactants in which the hydrophobicsection of the molecule carries no charge unless the pH is elevated toneutrality or above (e.g. carboxylic acids). Carboxylate, sulfonate,sulfate and phosphate are the polar (hydrophilic) solubilizing groupsfound in anionic surfactants. Of the cations (counter ions) associatedwith these polar groups, sodium, lithium and potassium impart watersolubility; ammonium and substituted ammonium ions provide both waterand oil solubility; and, calcium, barium, and magnesium promote oilsolubility. As those skilled in the art understand, anionics areexcellent detersive surfactants and are therefore favored additions toheavy duty detergent compositions.

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl) glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy) ether sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or condensation products of ethylene oxideand nonyl phenol (usually having 1 to 6 oxyethylene groups permolecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleicacid, and the like. Such carboxylates include alkyl ethoxy carboxylates,alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylatesurfactants and soaps (e.g. alkyl carboxyls). Secondary carboxylatesuseful in the present compositions include those which contain acarboxyl unit connected to a secondary carbon. The secondary carbon canbe in a ring structure, e.g. as in p-octyl benzoic acid, or as inalkyl-substituted cyclohexyl carboxylates. The secondary carboxylatesurfactants typically contain no ether linkages, no ester linkages andno hydroxyl groups. Further, they typically lack nitrogen atoms in thehead-group (amphiphilic portion). Suitable secondary soap surfactantstypically contain 11-13 total carbon atoms, although more carbons atoms(e.g., up to 16) can be present. Suitable carboxylates also includeacylamino acids (and salts), such as acylgluamates, acyl peptides,sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl tauratesand fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula:

R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂X  (3)

in which R is a C₈ to C₂₂ alkyl group or

in which R¹ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₅-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R¹ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R¹ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form. Commerciallyavailable carboxylates include, Neodox 23-4, a C₁₂₋₁₃ alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, a C₉ alkylarylpolyethoxy (10) carboxylic acid (Witco Chemical). Carboxylates are alsoavailable from Clariant, e.g. the product Sandopan® DTC, a C₁₃ alkylpolyethoxy (7) carboxylic acid.

Nonionic Surfactants

Useful nonionic surfactants are generally characterized by the presenceof an organic hydrophobic group and an organic hydrophilic group and aretypically produced by the condensation of an organic aliphatic, alkylaromatic or polyoxyalkylene hydrophobic compound with a hydrophilicalkaline oxide moiety which in common practice is ethylene oxide or apolyhydration product thereof, polyethylene glycol. Practically anyhydrophobic compound having a hydroxyl, carboxyl, amino, or amido groupwith a reactive hydrogen atom can be condensed with ethylene oxide, orits polyhydration adducts, or its mixtures with alkoxylenes such aspropylene oxide to form a nonionic surface-active agent. The length ofthe hydrophilic polyoxyalkylene moiety which is condensed with anyparticular hydrophobic compound can be readily adjusted to yield a waterdispersible or water soluble compound having the desired degree ofbalance between hydrophilic and hydrophobic properties. Useful nonionicsurfactants include:

1. Block polyoxypropylene-polyoxyethylene polymeric compounds based uponpropylene glycol, ethylene glycol, glycerol, trimethylolpropane, andethylenediamine as the initiator reactive hydrogen compound. Examples ofpolymeric compounds made from a sequential propoxylation andethoxylation of initiator are commercially available under the tradenames Pluronic® and Tetronic® manufactured by BASF Corp. Pluronic®compounds are difunctional (two reactive hydrogens) compounds formed bycondensing ethylene oxide with a hydrophobic base formed by the additionof propylene oxide to the two hydroxyl groups of propylene glycol. Thishydrophobic portion of the molecule weighs from about 1,000 to about4,000. Ethylene oxide is then added to sandwich this hydrophobe betweenhydrophilic groups, controlled by length to constitute from about 10% byweight to about 80% by weight of the final molecule. Tetronic® compoundsare tetra-flinctional block copolymers derived from the sequentialaddition of propylene oxide and ethylene oxide to ethylenediamine. Themolecular weight of the propylene oxide hydrotype ranges from about 500to about 7,000; and, the hydrophile, ethylene oxide, is added toconstitute from about 10% by weight to about 80% by weight of themolecule.

2. Condensation products of one mole of alkyl phenol wherein the alkylchain, of straight chain or branched chain configuration, or of singleor dual alkyl constituent, contains from about 8 to about 18 carbonatoms with from about 3 to about 50 moles of ethylene oxide. The alkylgroup can, for example, be represented by diisobutylene, di-amyl,polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactantscan be polyethylene, polypropylene, and polybutylene oxide condensatesof alkyl phenols. Examples of commercial compounds of this chemistry areavailable on the market under the trade names Igepal® manufactured byRhone-Poulene and Triton® manufactured by Union Carbide.

3. Condensation products of one mole of a saturated or unsaturated,straight or branched chain alcohol having from about 6 to about 24carbon atoms with from about 3 to about 50 moles of ethylene oxide. Thealcohol moiety can consist of mixtures of alcohols in the abovedelineated carbon range or it can consist of an alcohol having aspecific number of carbon atoms within this range. Examples of likecommercial surfactant are available under the trade names Neodol™manufactured by Shell Chemical Co. and Alfonic™ manufactured by VistaChemical Co.

4. Condensation products of one mole of saturated or unsaturated,straight or branched chain carboxylic acid having from about 8 to about18 carbon atoms with from about 6 to about 50 moles of ethylene oxide.The acid moiety can consist of mixtures of acids in the above definedcarbon atoms range or it can consist of an acid having a specific numberof carbon atoms within the range. Examples of commercial compounds ofthis chemistry are available on the market under the trade namesNopalcolm manufactured by Henkel Corporation and Lipopeg™ manufacturedby Lipo Chemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly calledpolyethylene glycol esters, other alkanoic acid esters formed byreaction with glycerides, glycerin, and polyhydric (saccharide orsorbitan/sorbitol) alcohols have application in this invention forspecialized embodiments, particularly indirect food additiveapplications. All of these ester moieties have one or more reactivehydrogen sites on their molecule which can undergo further acylation orethylene oxide (alkoxide) addition to control the hydrophilicity ofthese substances. Care must be exercised when adding these fatty esteror acylated carbohydrates to compositions of the present inventioncontaining amylase and/or lipase enzymes because of potentialincompatibility.

Examples of nonionic low foaming surfactants include:

5. Compounds from (1) which are modified, essentially reversed, byadding ethylene oxide to ethylene glycol to provide a hydrophile ofdesignated molecular weight; and, then adding propylene oxide to obtainhydrophobic blocks on the outside (ends) of the molecule. Thehydrophobic portion of the molecule weighs from about 1,000 to about3,100 with the central hydrophile including 10% by weight to about 80%by weight of the final molecule. These reverse Pluronics™ aremanufactured by BASF Corporation under the trade name Pluronic™surfactants. Likewise, the Tetronic™ R surfactants are produced by BASFCorporation by the sequential addition of ethylene oxide and propyleneoxide to ethylenediamine. The hydrophobic portion of the molecule weighsfrom about 2,100 to about 6,700 with the central hydrophile including10% by weight to 80% by weight of the final molecule.

6. Compounds from groups (1), (2), (3) and (4) which are modified by“capping” or “end blocking” the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce foaming by reaction with a smallhydrophobic molecule such as propylene oxide, butylene oxide, benzylchloride; and, short chain fatty acids, alcohols or alkyl halidescontaining from 1 to about 5 carbon atoms; and mixtures thereof. Alsoincluded are reactants such as thionyl chloride which convert terminalhydroxy groups to a chloride group. Such modifications to the terminalhydroxy group may lead to all-block, block-heteric, heteric-block orall-heteric nonionics.

Additional examples of effective low foaming nonionics include:

7. The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issuedSep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylenechain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is aninteger of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issuedAug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylenechains and hydrophobic oxypropylene chains where the weight of theterminal hydrophobic chains, the weight of the middle hydrophobic unitand the weight of the linking hydrophilic units each represent aboutone-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178issued May 7, 1968 to Lissant et al. having the general formulaZ[(OR)_(n)OH]_(z) wherein Z is alkoxylatable material, R is a radicalderived from an alkaline oxide which can be ethylene and propylene and nis an integer from, for example, 10 to 2,000 or more and z is an integerdetermined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,677,700, issued May 4, 1954 to Jackson et al. corresponding to theformula Y(C₃H₆O)_(n) (C₂H₄O)_(m)H wherein Y is the residue of organiccompound having from about 1 to 6 carbon atoms and one reactive hydrogenatom, n has an average value of at least about 6.4, as determined byhydroxyl number and m has a value such that the oxyethylene portionconstitutes about 10% to about 90% by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No.2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formulaY[(C₃H₆O_(n) (C₂H₄O)_(m)H]_(x) wherein Y is the residue of an organiccompound having from about 2 to 6 carbon atoms and containing x reactivehydrogen atoms in which x has a value of at least about 2, n has a valuesuch that the molecular weight of the polyoxypropylene hydrophobic baseis at least about 900 and m has value such that the oxyethylene contentof the molecule is from about 10% to about 90% by weight. Compoundsfalling within the scope of the definition for Y include, for example,propylene glycol, glycerine, pentaerythritol, trimethylolpropane,ethylenediamine and the like. The oxypropylene chains optionally, butadvantageously, contain small amounts of ethylene oxide and theoxyethylene chains also optionally, but advantageously, contain smallamounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which areadvantageously used in the compositions of this invention correspond tothe formula: P[(C₃H₆O)_(n)(C₂H₄O)_(m)H]_(x) wherein P is the residue ofan organic compound having from about 8 to 18 carbon atoms andcontaining x reactive hydrogen atoms in which x has a value of 1 or 2, nhas a value such that the molecular weight of the polyoxyethyleneportion is at least about 44 and m has a value such that theoxypropylene content of the molecule is from about 10% to about 90% byweight. In either case the oxypropylene chains may contain optionally,but advantageously, small amounts of ethylene oxide and the oxyethylenechains may contain also optionally, but advantageously, small amounts ofpropylene oxide.

8. Polyhydroxy fatty acid amide surfactants suitable for use in thepresent compositions include those having the structural formulaR₂CON_(R1)Z in which: R1 is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R₂ is aC₅-C₃₁ hydrocarbyl, which can be straight-chain; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z can be derived froma reducing sugar in a reductive amination reaction; such as a glycitylmoiety.

9. The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 0 to about 25 moles of ethylene oxide are suitable for use inthe present compositions. The alkyl chain of the aliphatic alcohol caneither be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms.

10. The ethoxylated C₆-C₁₈ fatty alcohols and C₆-C₁₈ mixed ethoxylatedand propoxylated fatty alcohols are suitable surfactants for use in thepresent compositions, particularly those that are water soluble.Suitable ethoxylated fatty alcohols include the C₆-Cis ethoxylated fattyalcohols with a degree of ethoxylation of from 3 to 50.

11. Suitable nonionic alkylpolysaccharide surfactants, particularly foruse in the present compositions include those disclosed in U.S. Pat. No.4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include ahydrophobic group containing from about 6 to about 30 carbon atoms and apolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10 saccharide units. Any reducing saccharidecontaining 5 or 6 carbon atoms can be used, e.g., glucose, galactose andgalactosyl moieties can be substituted for the glucosyl moieties.(Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc.positions thus giving a glucose or galactose as opposed to a glucosideor galactoside.) The intersaccharide bonds can be, e.g., between the oneposition of the additional saccharide units and the 2-, 3-, 4-, and/or6-positions on the preceding saccharide units.

12. Fatty acid amide surfactants suitable for use the presentcompositions include those having the formula: R₆CON(R₇)₂ in which R₆ isan alkyl group containing from 7 to 21 carbon atoms and each R₇ isindependently hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, or—(C₂H₄O)_(X)H, where x is in the range of from 1 to 3.

13. A useful class of non-ionic surfactants include the class defined asalkoxylated amines or, most particularly, alcoholalkoxylated/aminated/alkoxylated surfactants. These non-ionicsurfactants may be at least in part represented by the general formulae:R²⁰—(PO)_(S)N-(EO)_(t)H, R²⁰—(PO)_(S)N-(EO)_(t)H(EO)_(t)H, andR²⁰—N(EO)_(t)H; in which R²⁰ is an alkyl, alkenyl or other aliphaticgroup, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20,preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably2-5. Other variations on the scope of these compounds may be representedby the alternative formula: R²⁰—(PO)_(v)—N[(EO)_(w)H][(EO)_(z)H] inwhich R²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4(preferably 2)), and w and z are independently 1-10, preferably 2-5.These compounds are represented commercially by a line of products soldby Huntsman Chemicals as nonionic surfactants. A preferred chemical ofthis class includes Surfonic™ PEA 25 Amine Alkoxylate. Preferrednonionic surfactants for the compositions of the invention includealcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates,and the like.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 ofthe Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is anexcellent reference on the wide variety of nonionic compounds generallyemployed in the practice of the present invention. A typical listing ofnonionic classes, and species of these surfactants, is given in U.S.Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975.Further examples are given in “Surface Active Agents and detergents”(Vol. I and II by Schwartz, Perry and Berch).

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents are another classof nonionic surfactant useful in compositions of the present invention.Generally, semi-polar nonionics are high foamers and foam stabilizers,which can limit their application in CIP systems.

However, within compositional embodiments of this invention designed forhigh foam cleaning methodology, semi-polar nonionics would haveimmediate utility. The semi-polar nonionic surfactants include the amineoxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.

14. Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkalineor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20.

Useful water soluble amine oxide surfactants are selected from thecoconut or tallow alkyl di-(lower alkyl) amine oxides, specific examplesof which are dodecyldimethylamine oxide, tridecyldimethylamine oxide,etradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water solublephosphine oxides having the following structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R is an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 toabout 24 carbon atoms in chain length; and, R² and R³ are each alkylmoieties separately selected from alkyl or hydroxyalkyl groupscontaining 1 to 3 carbon atoms.

Examples of useful phosphine oxides include dimethyldecylphosphineoxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphoneoxide, dimethylhexadecylphosphine oxide,diethyl-2-hydroxyoctyldecylphosphine oxide,bis(2-hydroxyethyl)dodecylphosphine oxide, andbis(hydroxymethyl)tetradecylphosphine oxide.

Semi-polar nonionic surfactants useful herein also include the watersoluble sulfoxide compounds which have the structure:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹ is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbonatoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxylsubstituents; and R² is an alkyl moiety consisting of alkyl andhydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples of these sulfoxides include dodecyl methyl sulfoxide;3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methylsulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

Semi-polar nonionic surfactants for the compositions of the inventioninclude dimethyl amine oxides, such as lauryl dimethyl amine oxide,myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, combinationsthereof, and the like. Useful water soluble amine oxide surfactants areselected from the octyl, decyl, dodecyl, isododecyl, coconut, or tallowalkyl di-(lower alkyl) amine oxides, specific examples of which areoctyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamineoxide, undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers, such as the Pluronic andreverse Pluronic surfactants; alcohol alkoxylates, such as Dehypon LS-54(R-(EO)₅(PO)₄) and Dehypon LS-36 (R-(EO)₃(PO)₆); and capped alcoholalkoxylates, such as Plurafac LF221 and Tegoten EC11; mixtures thereof,or the like.

Defoaming Agent

The present invention includes a defoaming agent. Defoaming agentssuitable for use in the peroxycarboxylic acid compositions according tothe invention are compatible with the highly acidic peracid compositionsand anionic and/or nonionic surfactants which may be employed in theperacid compositions. The defoaming agents suitable for use in theperoxycarboxylic acid compositions according to the invention, maintaina low foam profile under various water conditions, preferably underdeionized or soft water conditions, and/or under mechanical action. In astill further aspect, the defoaming agents are compatible withsurfactants, preferably anionic surfactants, to achieve criticalperformance such as coupling/wetting, improved material compatibilityand enhanced biocidal efficacy. In preferred aspects, the defoamingagent provides a synergistic biocidal efficacy.

In an aspect of the invention, the defoaming agent is a metal salt,including for example, aluminum, magnesium, calcium, zinc and/or otherrare earth metal salts. In a preferred aspect, the defoaming agent is acation with high charge density, such as Fe³⁺, Al³⁺ and La³⁺. In apreferred aspect, the defoaming agent is aluminum sulfate.

In an aspect, the defoaming agent is not a transition metal compound,which are incompatible with the highly acidic equilibrium peracidcompositions according to the invention. In some embodiments, thecompositions of the present invention can include antifoaming agents ordefoamers which are of food grade quality given the application of themethod of the invention. In a further embodiment, the compositions ofthe present invention can include defoaming agents which are stable inacid environments (e.g. the peracid compositions containing a mineralacid and having a use solution pH of about 4 or less) and/or areoxidatively stable.

In an aspect of the invention, the defoaming agent can be used at anysuitable concentration to provide defoaming with the surfactantsaccording to the invention and to provide synergistic biocidal efficacy.In some embodiments, a concentrated equilibrium composition has aconcentration of the a defoaming agent from about 0.001 wt-% to about 10wt-%, or from about 0.1 wt-% to about 5 wt-%. In still otherembodiments, the defoaming agent has a concentration from about 0.1 wt-%to about 1 wt-%. Without limiting the scope of invention, the numericranges are inclusive of the numbers defining the range and include eachinteger within the defined range.

Fluorescent Active Compound

In an aspect, the present composition is a strongly acidic equilibriumperacid containing a fluorescent active compound that is stable in theperacid compositions according to the invention. In an aspect, thefluorescent active compound is formulated directly into the equilibriumperacid composition, instead of contained in a two or more part system(e.g. peracid precursors or preformed peracids with a fluorescent activecompound added prior to use and having short stability). In additionalaspects, the fluorescent active compound is further stable in andsuitable for use in other peracid compositions, including compositionsin concentrate and/or use solutions at both acidic and alkaline pHs. Forexample, in some aspects, the fluorescent active compound is furtherstable in highly acidic compositions (e.g. cleaning and sanitizingcompositions) and caustic compositions (e.g. laundry compositions). Infurther aspects, the fluorescent active compound is further stable instrongly oxidant systems (often employed for sanitizing compositions),such as chlorine.

In some aspects, the fluorescent active compound may be an inertcomponent of the composition (e.g. sanitizing compositions). In otheraspects, the fluorescent active compound is an active component of thecomposition (e.g. cleaning compositions).

In an aspect, the fluorescent active compound is an aryl sulfonate. Inother aspects, the fluorescent active compound is an alkyl arylsulfonate. In further aspects, the fluorescent active compound is anaromatic ring with a hydrophilic group (e.g. sulfonate, carboxylic).Without being limited to a particular theory or mechanism of theinvention, the inclusion of the hydrophilic group of the aromatic ringbeneficially results in the compatibility of the fluorescent activecompound with the peracid composition.

Exemplary suitable alkyl aryl sulfonates that can be used in thecompositions as fluorescent active compounds can have an alkyl groupthat contains 0 to 16 carbon atoms and the aryl group can be at leastone of benzene, diphenyl oxide, and/or naphthalene. A suitable alkylaryl sulfonate includes linear alkyl benzene sulfonate. A suitablelinear alkyl benzene sulfonate includes linear dodecyl benzyl sulfonatethat can be provided as an acid that is neutralized to form thesulfonate. Additional suitable alkyl aryl sulfonates include benzenesulfonate, toluene sulfonate, xylene sulfonate, cumene sulfonate,diphenyl oxide disulfonate, naphthalene sulfonate and naphthalenedisulfonates,

Additional exemplary suitable aromatic rings having a hydrophilic groupare shown in the following formulas:

In an aspect, the fluorescent active compound is sodium xylene sulfonate(SXS), such as is commercially available from the Stepan Company, and/orsodium cumene sulfonate (SCS), such as is commercially available fromAkzoNobel. In an aspect, the fluorescent active compound is sodium alkyldiphenyl disulfonate, such as commercially available from the DowCompany as Dowfax, such as Dowfax 2A1. In an aspect, the fluorescentactive compound is sodium naphthalene sulfonate and/or disodiumnaphthalene disulfonate, and or alkyl naphthalene sulfonate, such ascommercially available from AkzoNobel as PetroLBA.

In an aspect, the fluorescent active compound is suitable for indirectfood use. In a further aspect, the fluorescent active compound issuitable for more than only visual assessment of peracid concentrations(e.g. UV light source to confirm on a dry substrate a disinfectant wasapplied). Instead, the fluorescent active compounds are suitable fordose quantification by optical measurement.

Additional fluorescent tracers that may have applications of useaccording to the invention are commercially available under the tradename TRASAR® (Nalco Company® (Naperville, Ill.)) and/or may besynthesized using techniques known to persons of ordinary skill in theart of organic chemistry.

In an aspect of the invention, fluorescent active compound can be usedat any suitable concentration. In some embodiments, a concentratedequilibrium composition has a concentration of the fluorescent activecompound from about 0.001 wt-% to about 10 wt-%, or from about 0.1 wt-%to about 10 wt-%. In still other embodiments, the fluorescent activecompound has a concentration from about 0.5 wt-% to about 7.5 wt-%, ormore preferably from about 1 wt-% to about 5 wt-%. Without limiting thescope of invention, the numeric ranges are inclusive of the numbersdefining the range and include each integer within the defined range.

Methods of Delivery and Methods of Use

In an aspect, the present invention is directed to a method for storingand/or transporting a peroxycarboxylic acid composition, includingstoring the compositions, wherein at least about 80% of theperoxycarboxylic acid activity is retained after storage for anysuitable time under any suitable conditions, e.g., retaining at leastabout 80% of the peroxycarboxylic acid activity after storage of about30 days at about 50° C. Preferably, the methods include retaining atleast about 85%, at least about 90%, or at least about 95% or higher ofthe peroxycarboxylic acid activity after storage of about 30 days atabout 50° C.

In another aspect, the present invention is directed to a method fortransporting a peroxycarboxylic acid containing composition, whichmethod comprises transporting the compositions under ambient conditionswherein the SADT of the composition is at least about 45° C. duringtransportation. Preferably, the SADT of the composition is higher thanat least about 50° C., about 55° C., about 60° C., about 65° C. or about70° C. In a further aspect, the transporting of the peroxycarboxylicacid containing composition is in bulk e.g., 1,000 gallons and above.

In still another aspect, the present invention includes use of thecompositions for sanitizing surfaces and/or products. In another aspect,the compositions of the invention are particularly suitable for use as ahard surface sanitizer and/or disinfectant, a CIP sanitizer, food and/ortissue treatment sanitizer (including direct or indirect contactsanitizer), an environmental disinfectant, a laundry bleach anddisinfectant, and/or an indirect food contact sanitizer. The presentmethods can be used in the methods, processes or procedures describedand/or claimed in U.S. Pat. Nos. 5,200,189, 5,314,687, 5,718,910,6,165,483, 6,238,685B1, 8,017,409 and 8,236,573, each of which areherein incorporated by reference in their entirety.

The methods of use are suitable for treating a variety of surfaces,products and/or target. For example, these may include a food item or aplant item and/or at least a portion of a medium, a container, anequipment, a system or a facility for growing, holding, processing,packaging, storing, transporting, preparing, cooking or serving the fooditem or the plant item. The present methods can be used for treating anysuitable plant item. In some embodiments, the plant item is a grain,fruit, vegetable or flower plant item, a living plant item or aharvested plant item. In addition, the present methods can be used fortreating any suitable food item, e.g., an animal product, an animalcarcass or an egg, a fruit item, a vegetable item, or a grain item. Instill other embodiments, the food item may include a fruit, grain and/orvegetable item.

The present methods can be used for treating a target that is at least aportion of a container, an equipment, a system or a facility forholding, processing, packaging, storing, transporting, preparing,cooking or serving the food item or the plant item. In some embodiments,the target is at least a portion of a container, an equipment, a systemor a facility for holding, processing, packaging, storing, transporting,preparing, cooking or serving a meat item, a fruit item, a vegetableitem, or a grain item. In other embodiments, the target is at least aportion of a container, an equipment, a system or a facility forholding, processing, packaging, storing, or transporting an animalcarcass. In still other embodiments, the target is at least a portion ofa container, an equipment, a system or a facility used in foodprocessing, food service or health care industry. In yet otherembodiments, the target is at least a portion of a fixed in-placeprocess facility. An exemplary fixed in-place process facility cancomprise a milk line dairy, a continuous brewing system, a pumpable foodsystem or a beverage processing line.

The present methods can be used for treating a target that is at least aportion of a solid surface or liquid media. In some embodiments, thesolid surface is an inanimate solid surface. The inanimate solid surfacecan be contaminated by a biological fluid, e.g., a biological fluidcomprising blood, other hazardous body fluid, or a mixture thereof. Inother embodiments, the solid surface can be a contaminated surface. Anexemplary contaminated surface can comprise the surface of food servicewares or equipment, or the surface of a fabric.

The various methods of treatment can include the use of any suitablelevel of the peroxycarboxylic acid. In some embodiments, the treatedtarget composition comprises from about 10 ppm to about 1000 ppm of theperoxycarboxylic acid, including any of the peroxycarboxylic acidcompositions according to the invention.

In still another aspect, the present invention includes water treatmentmethods and other industrial processes uses of the compositions forsanitizing surfaces and/or products. In some aspects, the inventionincludes methods of using the peroxycarboxylic acid compositions toprevent biological fouling in various industrial processes andindustries, including oil and gas operations, to control microorganismgrowth, eliminate microbial contamination, limit or prevent biologicalfouling in liquid systems, process waters or on the surfaces ofequipment that come in contact with such liquid systems. As referred toherein, microbial contamination can occur in various industrial liquidsystems including, but not limited to, air-borne contamination, watermake-up, process leaks and improperly cleaned equipment. In anotheraspect, the peroxycarboxylic acid compositions are used to control thegrowth of microorganisms in water used in various oil and gasoperations. In a further aspect, the compositions are suitable forincorporating into fracturing fluids to control or eliminatemicroorganisms.

For the various industrial processes disclosed herein, “liquid system”refers to flood waters or an environment within at least one artificialartifact, containing a substantial amount of liquid that is capable ofundergoing biological fouling, it includes but is not limited toindustrial liquid systems, industrial water systems, liquid processstreams, industrial liquid process streams, industrial process watersystems, process water applications, process waters, utility waters,water used in manufacturing, water used in industrial services, aqueousliquid streams, liquid streams containing two or more liquid phases, andany combination thereof.

In at least one embodiment this technology would be applicable to anyprocess or utility liquid system where microorganisms are known to growand are an issue, and biocides are added. Examples of some industrialprocess water systems where the method of this invention could beapplied are in process water applications (flume water, shower water,washers, thermal processing waters, brewing, fermentation, CIP (clean inplace), hard surface sanitization, etc.), Ethanol/Bio-fuels processwaters, pretreatment and utility waters (membrane systems, ion-exchangebeds), water used in the process/manufacture of paper, ceiling tiles,fiber board, microelectronics, E-coat or electro depositionapplications, process cleaning, oil exploration and energy services(completion and work over fluids, drilling additive fluids, fracturingfluids, flood waters, etc.; oil fields—oil and gas wells/flow line,water systems, gas systems, etc.), and in particular water systems wherethe installed process equipment exhibits lowered compatibility tohalogenated biocides.

The methods by which the peroxycarboxylic acid compositions areintroduced into the aqueous fluids or liquid systems are not critical.Introduction of the peracid compositions may be carried out in acontinuous or intermittent manner and will depend on the type of waterand/or liquid being treated. In some embodiments, the peracidcompositions are introduced into an aqueous fluid according to themethods disclosed in U.S. patent application Ser. No. 13/645,671, titled“New Method and Arrangement for Feeding Chemicals into a HydrofracturingProcess and Oil and Gas Applications”, which is hereby incorporated byreference in its entirety.

Those skilled in the art will recognize, or be able to ascertain usingno more than routine experimentation, numerous equivalents to thespecific procedures, embodiments, claims, and examples described herein.Such equivalents are considered to be within the scope of this inventionand covered by the claims appended hereto. The contents of allreferences, patents, and patent applications cited throughout thisapplication are hereby incorporated by reference to the same extent asif each individual publication or patent application was specificallyand individually indicated as incorporated by reference. Allpublications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. The invention is further illustrated by thefollowing examples, which should not be construed as further limiting.

The various applications of use described herein provide theperoxycarboxylic acid compositions to a surface, liquid and/or productin need of antimicrobial and/or sanitizing treatment. Beneficially, thecompositions of the invention are fast-acting. However, the presentmethods require a certain minimal contact time of the compositions withthe surface, liquid and/or product in need of treatment for occurrenceof sufficient antimicrobial effect. The contact time can vary withconcentration of the use compositions, method of applying the usecompositions, temperature of the use compositions, pH of the usecompositions, amount of the surface, liquid and/or product to betreated, amount of soil or substrates on/in the surface, liquid and/orproduct to be treated, or the like. The contact or exposure time can beat least about 15 seconds. In some embodiments, the exposure time isabout 1 to 5 minutes. In other embodiments, the exposure time is atleast about 10 minutes, 30 minutes, or 60 minutes. In other embodiments,the exposure time is a few minutes to hours. In other embodiments, theexposure time is a few hours to days. The contact time will further varybased upon the concentration of peracid in a use solution.

The present methods can be conducted at any suitable temperature. Insome embodiments, the present methods are conducted at a temperatureranging from about 0° C. to about 70° C., e.g., from about 0° C. toabout 4° C. or 5° C., from about 5° C. to about 10° C., from about 11°C. to about 20° C., from about 21° C. to about 30° C., from about 31° C.to about 40° C., including at about 37° C., from about 41° C. to about50° C., from about 51° C. to about 60° C., or from about 61° C. to about70° C.

The compositions are suitable for antimicrobial efficacy against a broadspectrum of microorganisms, providing broad spectrum bactericidal andfungistatic activity. For example, the peracid biocides of thisinvention provide broad spectrum activity against wide range ofdifferent types of microorganisms (including both aerobic and anaerobicmicroorganisms), including bacteria, yeasts, molds, fungi, algae, andother problematic microorganisms.

The present methods can be used to achieve any suitable reduction of themicrobial population in and/or on the target or the treated targetcomposition. In some embodiments, the present methods can be used toreduce the microbial population in and/or on the target or the treatedtarget composition by at least one log₁₀. In other embodiments, thepresent methods can be used to reduce the microbial population in and/oron the target or the treated target composition by at least two log₁₀.In still other embodiments, the present methods can be used to reducethe microbial population in and/or on the target or the treated targetcomposition by at least three log₁₀.

The peroxycarboxylic acid compositions may include concentratecompositions or may be diluted to form use compositions. In general, aconcentrate refers to a composition that is intended to be diluted withwater to provide a use solution that contacts a surface, liquid and/orproduct in need of treatment to provide the desired cleaning, sanitizingor the like. The peroxycarboxylic acid composition that contacts thesurface, liquid and/or product in need of treatment can be referred toas a concentrate or a use composition (or use solution) dependent uponthe formulation employed in methods according to the invention. Itshould be understood that the concentration of the peroxycarboxylic acidin the composition will vary depending on whether the composition isprovided as a concentrate or as a use solution.

A use solution may be prepared from the concentrate by diluting theconcentrate with water at a dilution ratio that provides a use solutionhaving desired sanitizing and/or other antimicrobial properties. Thewater that is used to dilute the concentrate to form the use compositioncan be referred to as water of dilution or a diluent, and can vary fromone location to another. The typical dilution factor is betweenapproximately 1 and approximately 10,000 but will depend on factorsincluding water hardness, the amount of soil to be removed and the like.In an embodiment, the concentrate is diluted at a ratio of between about1:10 and about 1:10,000 concentrate to water. Particularly, theconcentrate is diluted at a ratio of between about 1:100 and about1:5,000 concentrate to water. More particularly, the concentrate isdiluted at a ratio of between about 1:250 and about 1:2,000 concentrateto water.

All publications and patent applications in this specification areindicative of the level of ordinary skill in the art to which thisinvention pertains. All publications and patent applications are hereinincorporated by reference to the same extent as if each individualpublication or patent application was specifically and individuallyindicated as incorporated by reference.

EXAMPLES

Embodiments of the present invention are further defined in thefollowing non-limiting Examples. It should be understood that theseExamples, while indicating certain embodiments of the invention, aregiven by way of illustration only. From the above discussion and theseExamples, one skilled in the art can ascertain the essentialcharacteristics of this invention, and without departing from the spiritand scope thereof, can make various changes and modifications of theembodiments of the invention to adapt it to various usages andconditions. Thus, various modifications of the embodiments of theinvention, in addition to those shown and described herein, will beapparent to those skilled in the art from the foregoing description.Such modifications are also intended to fall within the scope of theappended claims.

Example 1

Self-Accelerating Decomposition Test. As used herein, SADT refers to thelowest temperature at which self-accelerating decomposition may occurwith the peracid composition. In some embodiments, SADT refers to thelowest temperature at which self-accelerating decomposition may occurunder the commercial packaging, storage, transportation and/or usecondition(s). SADT can be estimated, calculated, predicted and/ormeasured by any suitable methods. For example, SADT can be estimated, ormeasured directly by one of 3 methods (H1, H2 and H4) recommended by theUN Committee for the Transportation of Dangerous Goods in“Recommendations on the Transport of Dangerous Goods, Model Regulations”(Rev.17) ST/SG/AC.10/1/Rev.17. For example, the methodology disclosed inMalow and Wehrstedt, J. Hazard Mater., 120(1-3):21-4 (2005) can be used,which is herein incorporated by reference in its entirety.

The full test protocol used in this Example is available at“Recommendations on the Transport of Dangerous Goods,” Manual of Testsand Criteria, 5th revised edition: (United Nations): Classificationprocedures, test methods and criteria relating to self-reactivesubstances of Division 4.1 and organic peroxides of Division 5.2: TestH.4 Heat accumulation storage test (28.4.4).

Since peroxycarboxylic acids fall into the organic peroxidesclassification and therefore are self-reactive, self-heating products,testing was conducted to demonstrate if cooling is required for a givenpackage of a peroxycarboxylic acid product. One of the four publishedrecommended methods of the UN Committee for the Transport of DangerousGoods allows the modeling of a large volume package with Dewar flasks.Again, this method is utilized to model large commercial packages whichif tested directly (i.e. with the H1 method) might pose a significanthazard as well as inconvenience due to size. In this example the productwas intended to be sold in 1000 L plastic tanks known as totes and itwas necessary to determine if the SADT was greater or less than 45° C.If it was found to be less than 45° C. refrigeration would be requiredboth in shipping and in storage and use thus severely limiting theproducts potential for a wide application in the marketplace.Additionally if the product has an SADT equal to or less than 50° C. theproduct is not permitted to be shipped stored or used in conatainers aslarge as 1000 L but is essentially limited to 200 L drums or smaller,again severely limiting the products applicationsA 1 L cylindrical Dewarflask is fitted with a closure that causes it to cool at the same rateas the 1000 L polyethylene tank. The Dewar flask is filled to 80% offull volume with the product, fitted with the specific closure and arecording thermometer, and is placed in an oven set at 45° C. Once theinternal package temperature warms to 43° C. temperature, time recordingis begun. If the temperature exceeds the oven temp of 45° C. by amagnitude of 6° C. (51° C.) before 7 days have elapsed the SADT for theproduct in that 1000 L package is defined as <45° C. and the product isdeemed to require cooling. As such a requirement can severely limit useof a product in many industries, this SADT is considered an unfavorableproperty. If the temperature doesn't exceed a 6° C. rise over the oventemperature the SADT is deemed >45° C. and may be considered forshipping and storage in that 1000 L package without refrigeration.

The H4 test methodology was employed at 50° C. The testedperoxycarboxylic acid compositions are shown in Table 2.

TABLE 2 Wt % DPA HEDP Composition Formula Formula DPA   0.05  0.0 HEDP(60%)  0.0  1.5 Sulfonated oleic  1-10  1-10 acid (70%) Octanoic acid 1-10  1-10 Acetic acid  2-20  2-20 Sodium xylene  3-20  3-20 sulfonate(40%) Sodium cumene 1-5 1-5 sulfonate (96%) H₂O₂ (35%) 10-50 10-50Al₂(SO₄)₃•18H₂O 1-5 1-5 H₂SO₄ (96%)  12.5  12.5 Deionized Water 20-5020-50 Total 100.0 100.0

The resulting SADT from the evaluated formulations is shown in FIG. 1.While the formulae were identical aside from their stabilizers, theDPA-stabilized peracid composition showed a much more gradual increasein temperature (below the SADT of the peracid) demonstrating suitabilityfor stabilization for transportation and/or storag. In contrast, thephosphate/HEDP-stabilized peracid composition showed excessive increasein temperature in the first day, necessitating the termination of theexperiment to avoid explosion of the composition/container. The resultsillustrate an advantage in DPA stabilization in a high acid environment.

Example 2

The methods of Example 1 were further employed to analyze the SADT of afatty peracid, a peroxyoctanoic acid compositions having an even furtherincreased acidity. While the formulae were identical aside from theirstabilizers, the results again illustrate an advantage in DPAstabilization in a high acid environment that extends to fatty peracidssuch as peroxy octanoic acid.

TABLE 3 Wt % HEDP DPA Composition Formula Formula DPA  0.0   0.05 HEDP(60%)   2.54  0.0 Octanoic acid  1-10  1-10 Sodium octane 10-30 10-30sulfonate (40%) H₂O₂ (35%) 10-50 10-50 H₂SO₄ (96%)  14.14  14.14Deionized Water 20-50 20-50 Total 100.0 100.0

The resulting SADT from the evaluated formulations is shown in FIG. 2.The DPA-stabilized peracid composition, even under increased acidity ofthe peracid composition, showed a much more gradual increase intemperature (below the SADT of the peracid) in comparison to thephosphate/HEDP-stabilized peracid composition. The DPA-stabilizedperacid composition would likely meet DOT standards for transportationsince its temperature projected out to 7 days since reaching 48° C.would likely not exceed 56° C.

Example 3

As set forth in Table 4 (and shown in FIG. 3) a strong acid containing areduced hydrogen peroxide concentration was evaluated by the H4-SADTprotocol in a Dewar flask modeling a 300 gallon IBC or plastic tote.

TABLE 4 Composition Wt % DPA   0.05 HEDP (60%)  0.0 Sulfonated oleic 1-10 acid (70%) Octanoic acid  1-10 Acetic acid  2-20 Sodium xylene 1-5sulfonate (40%) Sodium cumene 1-5 sulfonate (96%) H₂O₂ (35%) 35 Al₂(SO₄) 3•18H2O 0.05-2.0  H₂SO₄ (96%) 18  Deionized Water 20-50 Total100.0

The evaluation of the stability of the composition was conducted anddespite the presence of the 17% sulfuric acid, the compositioncontaining the DPA stabilizing agent was stabilized. The stabilizationof the composition, as shown in FIG. 3, illustrates the stabilization ofthe solution temperature only exceeding the 50° C. ambient temperatureby 4.7° C. by day 7. Beneficially, these results qualify the highlyacidic peracid composition for shipping and storage in a 300 gallon totewithout refrigeration, demonstrating a significant improvement over theinstability of HEDP-containing equivalent peracid compositions.

Example 4

The methods of Example 1 were further employed to analyze the SADT of afatty peracid, a peroxyoctanoic acid compositions with an HEDPstabilizer, in comparison to an equivalent peracid composition with aDPA stabilizer, as shown in Table 5.

TABLE 5 Wt % Formula Formula Composition HEDP stabilizer with DPAstabilizer DPA  0.0   0.05 HEDP (60%)   2.54  0.0 Octanoic acid  1-10 1-10 Sodium octane 10-30 10-30 sulfonate (40%) H2O2 (35%)  23.00  23.00H2SO4 (96%)  14.14  14.14 Deionized Water 20-50 20-50 Total 100.0 100.0

The evaluation of the stability of the composition was conducted anddespite the presence of the 14% sulfuric acid, the compositioncontaining the DPA stabilizing agent according to embodiments of theinvention was stabilized whereas the formula containing only an HEDPstabilizer failed prior to the 7^(th) day. The stabilization of thecomposition, as shown in FIG. 4, illustrates the stabilization of thesolution temperature only exceeding the 50° C. ambient temperature by2.8° C. by day 7. Again, these results qualify the highly acidic peracidcomposition stabilized by the DPA stabilizing agent for shipping andstorage in a 300 gallon tote without refrigeration. This demonstrates asignificant improvement over the instability of HEDP-containingequivalent peracid compositions.

The inventions being thus described, it will be obvious that the samemay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the inventions and all suchmodifications are intended to be included within the scope of thefollowing claims. The above specification provides a description of themanufacture and use of the disclosed compositions and methods. Sincemany embodiments can be made without departing from the spirit and scopeof the invention, the invention resides in the claims.

1-20. (canceled) 21: A method for non-refrigeration transport of aperoxycarboxylic acid composition, comprising: stabilizing theperoxycarboxylic acid composition with a stabilizing agent thatincreases self-accelerating decomposition temperature (SADT) of theperoxycarboxylic acid to form a stabilized peroxycarboxylic acidcomposition having a SADT of at least about 45° C., wherein thestabilized peroxycarboxylic acid composition comprises (1) a C₁-C₂₂peroxycarboxylic acid; (2) a C₁-C₂₂ carboxylic acid; (3) hydrogenperoxide; (4) from about 1 wt-% to about 50 wt-% of a strong acid; and(5) the stabilizing agent, wherein the stabilizing agent comprises apicolinic acid or a compound having the following Formula (IA):

wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b) areindependently hydrogen or (C₁-C₆)alkyl; wherein R² is OH or—NR^(2a)R^(2b), wherein R^(2a) and R^(2b) are independently hydrogen or(C₁-C₆)alkyl; wherein each R³ is independently (C₁-C₆)alkyl,(C₂-C₆)alkenyl or (C₂-C₆)alkynyl; and n is a number from zero to 3; or asalt thereof, or a compound having the following Formula (IB):

wherein R¹ is OH or —NR^(1a)R^(1b) wherein R^(1a) and R^(1b) areindependently hydrogen or (C₁-C₆)alkyl; wherein R² is OH or—NR^(2a)R^(2b), wherein R^(2a) and R^(2b) are independently hydrogen or(C₁-C₆)alkyl; wherein each R³ is independently (C₁-C₆)alkyl,(C₂-C₆)alkenyl or (C₂-C₆)alkynyl; and n is a number from zero to 3; or asalt thereof; and transporting the stabilized peroxycarboxylic acidcomposition, wherein the transporting does not require refrigeration andthe SADT provides for an exemption from U.S. Department ofTransportation (DOT) UN 5.2 classification and allows for thetransporting of the stabilized peroxycarboxylic acid compositionaccording to reduced risk DOT UN 5.1 classification. 22: The method ofclaim 21, wherein transporting comprises transporting the stabilizedperoxycarboxylic acid composition under ambient conditions. 23: Themethod of claim 21, wherein the stabilized peroxycarboxylic acidcomposition is transported in bulk at a volume of 300 gallons or more.24: The method of claim 21, wherein the stabilized peroxycarboxylic acidcomposition is transported in bulk at a volume of 1000 gallons or more.25: The method of claim 21, wherein the C₁-C₂₂ peroxycarboxylic acidcomprises from about 0.1 wt-% to about 40 wt-%, the C₁-C₂₂ carboxylicacid comprises from about 0.1 wt-% to about 90 wt-%, the hydrogenperoxide comprises from about 1 wt-% to about 90 wt-%, and thestabilizing agent comprises from about 0.001 wt-% to about 25 wt-%. 26:The method of claim 21, wherein the stabilized peroxycarboxylic acidcomposition further comprises at least one additional agent comprisingan anionic surfactant, a hydrotrope, a defoaming agent, a solvent, afluorescent active agent, or combinations thereof. 27: The method ofclaim 26, wherein the additional agent is a hydrotrope that aids insolubilization of the stabilizing agent. 28: The method of claim 21,wherein the strong acid comprises sulfuric acid, phosphoric acid,methane sulfonic acid, or combinations thereof. 29: The method of claim21, wherein the C₁-C₂₂ peroxycarboxylic acid is a C₂-C₂₀peroxycarboxylic acid comprising peroxyacetic acid, peroxyoctanoic acid,peroxysulfonated oleic acid, or combinations thereof, wherein the C₁-C₂₂carboxylic acid is a C₂-C₂₀ carboxylic acid comprising acetic acid,octanoic acid, sulfonated oleic acid, or combinations thereof, andwherein the stabilizing agent is a picolinic acid, or a salt thereof.30: The method of claim 21, wherein the stabilizing agent is2,6-pyridinedicarboxylic acid, or a salt thereof. 31: The method ofclaim 21, wherein the stabilized peroxycarboxylic acid composition has ause solution pH below about
 4. 32: The method of claim 21, wherein thecomposition further comprises 1-hydroxyethylidene-1, 1-diphosphonic acid(HEDP). 33: The method of claim 24, wherein the SADT of the stabilizedperoxycarboxylic acid composition is at least about 50° C., at leastabout 55° C., at least about 60° C., at least about 65° C., or at leastabout 70° C. 34: The method of claim 21, wherein the stabilizedperoxycarboxylic acid composition is transported in a plastic tote ortank. 35: The method of claim 23, wherein the stabilizedperoxycarboxylic acid composition is transported in a plastic tote ortank. 36: The method of claim 21, wherein the SADT is determinedaccording to one of H1, H2, or H4 heat accumulation storage testrecommended by the United Nations Committee for Transportation ofDangerous Goods, Model Regulations (Rev. 17). 37: A method fornon-refrigeration storage of a peroxycarboxylic acid composition,comprising: stabilizing the peroxycarboxylic acid composition with astabilizing agent that increases self-accelerating decompositiontemperature (SADT) of the peroxycarboxylic acid to form a stabilizedperoxycarboxylic acid composition having a SADT of at least about 45°C., wherein the stabilized peroxycarboxylic acid composition comprises(1) a C₁-C₂₂ peroxycarboxylic acid; (2) a C₁-C₂₂ carboxylic acid; (3)hydrogen peroxide; (4) from about 1 wt-% to about 50 wt-% of a strongacid; and (5) the stabilizing agent, wherein the stabilizing agentcomprises a picolinic acid or a compound having the following Formula(IA):

wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b) areindependently hydrogen or (C₁-C₆)alkyl; wherein R² is OH or—NR^(2a)R^(2b), wherein R^(2a) and R^(2b) are independently hydrogen or(C₁-C₆)alkyl; wherein each R³ is independently (C₁-C₆)alkyl,(C₂-C₆)alkenyl or (C₂-C₆)alkynyl; and n is a number from zero to 3; or asalt thereof, or a compound having the following Formula (IB):

wherein R¹ is OH or —NR^(1a)R^(1b), wherein R^(1a) and R^(1b) areindependently hydrogen or (C₁-C₆)alkyl; wherein R² is OH or—NR^(2a)R^(2b), wherein R^(2a) and R^(2b) are independently hydrogen or(C₁-C₆)alkyl; wherein each R³ is independently (C₁-C₆)alkyl,(C₂-C₆)alkenyl or (C₂-C₆)alkynyl; and n is a number from zero to 3; or asalt thereof; and storing the stabilized peroxycarboxylic acidcomposition, wherein the storing does not require refrigeration and isunder ambient conditions. 38: The method of claim 37, wherein thestabilized peroxycarboxylic acid composition is stored in bulk at avolume of 300 gallons or more. 39: The method of claim 37, wherein theC₁-C₂₂ peroxycarboxylic acid comprises from about 0.1 wt-% to about 40wt-%, the C₁-C₂₂ carboxylic acid comprises from about 0.1 wt-% to about90 wt-%, the hydrogen peroxide comprises from about 1 wt-% to about 90wt-%, and the stabilizing agent comprises from about 0.001 wt-% to about25 wt-%. 40: The method of claim 37, wherein the stabilizedperoxycarboxylic acid composition further comprises at least oneadditional agent comprising an anionic surfactant, a hydrotrope, adefoaming agent, a solvent, a fluorescent active agent, or combinationsthereof. 41: The method of claim 40, wherein the additional agent is ahydrotrope that aids in solubilization of the stabilizing agent. 42: Themethod of claim 37, wherein the strong acid comprises sulfuric acid,phosphoric acid, methane sulfonic acid, or combinations thereof. 43: Themethod of claim 37, wherein the C₁-C₂₂ peroxycarboxylic acid is a C₂-C₂₀peroxycarboxylic acid comprising peroxyacetic acid, peroxyoctanoic acid,peroxysulfonated oleic acid, or combinations thereof, wherein the C₁-C₂₂carboxylic acid is a C₂-C₂₀ carboxylic acid comprising acetic acid,octanoic acid, sulfonated oleic acid, or combinations thereof, andwherein the stabilizing agent is a picolinic acid, or a salt thereof.44: The method of claim 37, wherein the stabilizing agent is2,6-pyridinedicarboxylic acid, or a salt thereof. 45: The method ofclaim 37, wherein the stabilized peroxycarboxylic acid composition has ause solution pH below about
 4. 46: The method of claim 37, wherein thecomposition further comprises 1-hydroxyethylidene-1, 1-diphosphonic acid(HEDP). 47: The method of claim 38, wherein the SADT of the stabilizedperoxycarboxylic acid composition is at least about 50° C., at leastabout 55° C., at least about 60° C., at least about 65° C., or at leastabout 70° C. 48: The method of claim 37, wherein the stabilizedperoxycarboxylic acid composition is stored in a plastic tote or tank.49: The method of claim 38, wherein the stabilized peroxycarboxylic acidcomposition is stored in a plastic tote or tank. 50: The method of claim37, wherein the SADT is determined according to one of H1, H2, or H4heat accumulation storage test recommended by the United NationsCommittee for Transportation of Dangerous Goods, Model Regulations (Rev.17).